JP2004506030A - New aroma compounds - Google Patents
New aroma compounds Download PDFInfo
- Publication number
- JP2004506030A JP2004506030A JP2002519343A JP2002519343A JP2004506030A JP 2004506030 A JP2004506030 A JP 2004506030A JP 2002519343 A JP2002519343 A JP 2002519343A JP 2002519343 A JP2002519343 A JP 2002519343A JP 2004506030 A JP2004506030 A JP 2004506030A
- Authority
- JP
- Japan
- Prior art keywords
- methylpropyl
- alkene
- methyl
- mixture
- methylcyclohexanol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 150000001875 compounds Chemical class 0.000 title abstract description 9
- 150000001336 alkenes Chemical class 0.000 claims abstract description 38
- 239000003205 fragrance Substances 0.000 claims abstract description 16
- PMKDAPPYGOWKLX-UHFFFAOYSA-N 1-methyl-3-(2-methylpropyl)cyclohexan-1-ol Chemical compound CC(C)CC1CCCC(C)(O)C1 PMKDAPPYGOWKLX-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims description 24
- HVXJSUYYVZSAIW-UHFFFAOYSA-N 1-methoxy-2-methyl-4-(2-methylpropyl)cyclohexane Chemical compound COC1CCC(CC(C)C)CC1C HVXJSUYYVZSAIW-UHFFFAOYSA-N 0.000 claims description 8
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- UDPKUAIUDYPHMS-UHFFFAOYSA-N 2-methyl-4-(2-methylpropyl)cyclohexan-1-ol Chemical compound CC(C)CC1CCC(O)C(C)C1 UDPKUAIUDYPHMS-UHFFFAOYSA-N 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 238000003379 elimination reaction Methods 0.000 claims description 4
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 230000000887 hydrating effect Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 6
- 239000002304 perfume Substances 0.000 abstract description 5
- 239000000543 intermediate Substances 0.000 abstract description 4
- 239000012437 perfumed product Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 21
- 239000012043 crude product Substances 0.000 description 9
- 238000004821 distillation Methods 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000005984 hydrogenation reaction Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- LKLHOBBPUDWOTB-UHFFFAOYSA-N 1-methyl-3-(2-methylpropyl)cyclohexene Chemical compound CC(C)CC1CCCC(C)=C1 LKLHOBBPUDWOTB-UHFFFAOYSA-N 0.000 description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- RALZXSLYVAGXGC-UHFFFAOYSA-N 1-methyl-5-(2-methylpropyl)cyclohexene Chemical compound CC(C)CC1CCC=C(C)C1 RALZXSLYVAGXGC-UHFFFAOYSA-N 0.000 description 5
- 241000402754 Erythranthe moschata Species 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- -1 ketals Chemical class 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- SMZJZKJNSUMTNX-UHFFFAOYSA-N 1-methylidene-3-(2-methylpropyl)cyclohexane Chemical compound CC(C)CC1CCCC(=C)C1 SMZJZKJNSUMTNX-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000000796 flavoring agent Substances 0.000 description 4
- 235000019634 flavors Nutrition 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000006210 lotion Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000012258 stirred mixture Substances 0.000 description 4
- QHPRKIGPJCLWAM-UHFFFAOYSA-N 1-(4-methoxy-3-methylphenyl)-2-methylpropan-1-one Chemical compound COC1=CC=C(C(=O)C(C)C)C=C1C QHPRKIGPJCLWAM-UHFFFAOYSA-N 0.000 description 3
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229940022663 acetate Drugs 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003599 detergent Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 238000004508 fractional distillation Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- DTFKRVXLBCAIOZ-UHFFFAOYSA-N 2-methylanisole Chemical compound COC1=CC=CC=C1C DTFKRVXLBCAIOZ-UHFFFAOYSA-N 0.000 description 2
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- ZCTQGTTXIYCGGC-UHFFFAOYSA-N Benzyl salicylate Chemical compound OC1=CC=CC=C1C(=O)OCC1=CC=CC=C1 ZCTQGTTXIYCGGC-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- GLZPCOQZEFWAFX-UHFFFAOYSA-N Geraniol Chemical compound CC(C)=CCCC(C)=CCO GLZPCOQZEFWAFX-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- IGODOXYLBBXFDW-UHFFFAOYSA-N alpha-Terpinyl acetate Chemical compound CC(=O)OC(C)(C)C1CCC(C)=CC1 IGODOXYLBBXFDW-UHFFFAOYSA-N 0.000 description 2
- QUKGYYKBILRGFE-UHFFFAOYSA-N benzyl acetate Chemical compound CC(=O)OCC1=CC=CC=C1 QUKGYYKBILRGFE-UHFFFAOYSA-N 0.000 description 2
- SESFRYSPDFLNCH-UHFFFAOYSA-N benzyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCC1=CC=CC=C1 SESFRYSPDFLNCH-UHFFFAOYSA-N 0.000 description 2
- QMVPMAAFGQKVCJ-UHFFFAOYSA-N citronellol Chemical compound OCCC(C)CCC=C(C)C QMVPMAAFGQKVCJ-UHFFFAOYSA-N 0.000 description 2
- JOZKFWLRHCDGJA-UHFFFAOYSA-N citronellol acetate Chemical compound CC(=O)OCCC(C)CCC=C(C)C JOZKFWLRHCDGJA-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- HFJRKMMYBMWEAD-UHFFFAOYSA-N dodecanal Chemical compound CCCCCCCCCCCC=O HFJRKMMYBMWEAD-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- RRAFCDWBNXTKKO-UHFFFAOYSA-N eugenol Chemical compound COC1=CC(CC=C)=CC=C1O RRAFCDWBNXTKKO-UHFFFAOYSA-N 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- PQNFLJBBNBOBRQ-UHFFFAOYSA-N indane Chemical compound C1=CC=C2CCCC2=C1 PQNFLJBBNBOBRQ-UHFFFAOYSA-N 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- CDOSHBSSFJOMGT-UHFFFAOYSA-N linalool Chemical compound CC(C)=CCCC(C)(O)C=C CDOSHBSSFJOMGT-UHFFFAOYSA-N 0.000 description 2
- UWKAYLJWKGQEPM-LBPRGKRZSA-N linalyl acetate Chemical compound CC(C)=CCC[C@](C)(C=C)OC(C)=O UWKAYLJWKGQEPM-LBPRGKRZSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- MDHYEMXUFSJLGV-UHFFFAOYSA-N phenethyl acetate Chemical compound CC(=O)OCCC1=CC=CC=C1 MDHYEMXUFSJLGV-UHFFFAOYSA-N 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- HLCSDJLATUNSSI-JXMROGBWSA-N (2e)-3,7-dimethylocta-2,6-dienenitrile Chemical compound CC(C)=CCC\C(C)=C\C#N HLCSDJLATUNSSI-JXMROGBWSA-N 0.000 description 1
- VSRVCSJJKWDZSH-UHFFFAOYSA-N (3-pentyloxan-4-yl) acetate Chemical compound CCCCCC1COCCC1OC(C)=O VSRVCSJJKWDZSH-UHFFFAOYSA-N 0.000 description 1
- 239000001490 (3R)-3,7-dimethylocta-1,6-dien-3-ol Substances 0.000 description 1
- VCOCESNMLNDPLX-BTXGZQJSSA-N (3s,6s)-2,2,8,8-tetramethyl-octahydro-1h-2,4a-methanonapthalene-10-one Chemical compound O=C1CCC(C)(C)[C@@]2(C3)C1C(C)(C)[C@H]3CC2 VCOCESNMLNDPLX-BTXGZQJSSA-N 0.000 description 1
- 239000001724 (4,8-dimethyl-2-propan-2-ylidene-3,3a,4,5,6,8a-hexahydro-1H-azulen-6-yl) acetate Substances 0.000 description 1
- QMVPMAAFGQKVCJ-SNVBAGLBSA-N (R)-(+)-citronellol Natural products OCC[C@H](C)CCC=C(C)C QMVPMAAFGQKVCJ-SNVBAGLBSA-N 0.000 description 1
- CDOSHBSSFJOMGT-JTQLQIEISA-N (R)-linalool Natural products CC(C)=CCC[C@@](C)(O)C=C CDOSHBSSFJOMGT-JTQLQIEISA-N 0.000 description 1
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 description 1
- VPKMGDRERYMTJX-CMDGGOBGSA-N 1-(2,6,6-Trimethyl-2-cyclohexen-1-yl)-1-penten-3-one Chemical compound CCC(=O)\C=C\C1C(C)=CCCC1(C)C VPKMGDRERYMTJX-CMDGGOBGSA-N 0.000 description 1
- NGLUZUGEANBMSM-UHFFFAOYSA-N 1-methoxy-2-methyl-4-(2-methylpropyl)benzene Chemical compound COC1=CC=C(CC(C)C)C=C1C NGLUZUGEANBMSM-UHFFFAOYSA-N 0.000 description 1
- ZGVQPESUNXFUMQ-UHFFFAOYSA-N 1-methyl-3-(2-methylpropyl)cyclohexane Chemical compound CC(C)CC1CCCC(C)C1 ZGVQPESUNXFUMQ-UHFFFAOYSA-N 0.000 description 1
- CTMHWPIWNRWQEG-UHFFFAOYSA-N 1-methylcyclohexene Chemical compound CC1=CCCCC1 CTMHWPIWNRWQEG-UHFFFAOYSA-N 0.000 description 1
- FYERTDTXGGOMGT-UHFFFAOYSA-N 2,2-diethoxyethylbenzene Chemical compound CCOC(OCC)CC1=CC=CC=C1 FYERTDTXGGOMGT-UHFFFAOYSA-N 0.000 description 1
- WNJSKZBEWNVKGU-UHFFFAOYSA-N 2,2-dimethoxyethylbenzene Chemical compound COC(OC)CC1=CC=CC=C1 WNJSKZBEWNVKGU-UHFFFAOYSA-N 0.000 description 1
- BEARMGATPGLSKG-UHFFFAOYSA-N 2,6-dimethyloct-7-en-2-yl acetate Chemical compound C=CC(C)CCCC(C)(C)OC(C)=O BEARMGATPGLSKG-UHFFFAOYSA-N 0.000 description 1
- GQDUXZKNWUFJLT-UHFFFAOYSA-N 2-(2-pentylcyclopentyl)acetic acid Chemical compound CCCCCC1CCCC1CC(O)=O GQDUXZKNWUFJLT-UHFFFAOYSA-N 0.000 description 1
- ROKSAUSPJGWCSM-UHFFFAOYSA-N 2-(7,7-dimethyl-4-bicyclo[3.1.1]hept-3-enyl)ethanol Chemical compound C1C2C(C)(C)C1CC=C2CCO ROKSAUSPJGWCSM-UHFFFAOYSA-N 0.000 description 1
- PJXHBTZLHITWFX-UHFFFAOYSA-N 2-heptylcyclopentan-1-one Chemical compound CCCCCCCC1CCCC1=O PJXHBTZLHITWFX-UHFFFAOYSA-N 0.000 description 1
- RIWRBSMFKVOJMN-UHFFFAOYSA-N 2-methyl-1-phenylpropan-2-ol Chemical compound CC(C)(O)CC1=CC=CC=C1 RIWRBSMFKVOJMN-UHFFFAOYSA-N 0.000 description 1
- BJLRAKFWOUAROE-UHFFFAOYSA-N 2500-83-6 Chemical compound C12C=CCC2C2CC(OC(=O)C)C1C2 BJLRAKFWOUAROE-UHFFFAOYSA-N 0.000 description 1
- DLHQZZUEERVIGQ-UHFFFAOYSA-N 3,7-dimethyl-3-octanol Chemical compound CCC(C)(O)CCCC(C)C DLHQZZUEERVIGQ-UHFFFAOYSA-N 0.000 description 1
- MTDAKBBUYMYKAR-UHFFFAOYSA-N 3,7-dimethyloct-6-enenitrile Chemical compound N#CCC(C)CCC=C(C)C MTDAKBBUYMYKAR-UHFFFAOYSA-N 0.000 description 1
- GOLORTLGFDVFDW-UHFFFAOYSA-N 3-(1h-benzimidazol-2-yl)-7-(diethylamino)chromen-2-one Chemical compound C1=CC=C2NC(C3=CC4=CC=C(C=C4OC3=O)N(CC)CC)=NC2=C1 GOLORTLGFDVFDW-UHFFFAOYSA-N 0.000 description 1
- BWVZAZPLUTUBKD-UHFFFAOYSA-N 3-(5,6,6-Trimethylbicyclo[2.2.1]hept-1-yl)cyclohexanol Chemical compound CC1(C)C(C)C2CC1CC2C1CCCC(O)C1 BWVZAZPLUTUBKD-UHFFFAOYSA-N 0.000 description 1
- INIOTLARNNSXAE-UHFFFAOYSA-N 4,8-dimethyl-2-propan-2-ylidene-3,3a,4,5,6,8a-hexahydro-1h-azulen-6-ol Chemical compound CC1CC(O)C=C(C)C2CC(=C(C)C)CC12 INIOTLARNNSXAE-UHFFFAOYSA-N 0.000 description 1
- JMOOXVHSTRFQQH-UHFFFAOYSA-N 4-(2-methylpentan-3-yl)cyclohex-3-ene-1-carbaldehyde Chemical compound CCC(C(C)C)C1=CCC(C=O)CC1 JMOOXVHSTRFQQH-UHFFFAOYSA-N 0.000 description 1
- ORMHZBNNECIKOH-UHFFFAOYSA-N 4-(4-hydroxy-4-methylpentyl)cyclohex-3-ene-1-carbaldehyde Chemical compound CC(C)(O)CCCC1=CCC(C=O)CC1 ORMHZBNNECIKOH-UHFFFAOYSA-N 0.000 description 1
- HIQIXEFWDLTDED-UHFFFAOYSA-N 4-hydroxy-1-piperidin-4-ylpyrrolidin-2-one Chemical compound O=C1CC(O)CN1C1CCNCC1 HIQIXEFWDLTDED-UHFFFAOYSA-N 0.000 description 1
- MBZRJSQZCBXRGK-UHFFFAOYSA-N 4-tert-Butylcyclohexyl acetate Chemical compound CC(=O)OC1CCC(C(C)(C)C)CC1 MBZRJSQZCBXRGK-UHFFFAOYSA-N 0.000 description 1
- LJSJTXAZFHYHMM-UHFFFAOYSA-N 7-methyloctyl acetate Chemical compound CC(C)CCCCCCOC(C)=O LJSJTXAZFHYHMM-UHFFFAOYSA-N 0.000 description 1
- QGFSQVPRCWJZQK-UHFFFAOYSA-N 9-Decen-1-ol Chemical compound OCCCCCCCCC=C QGFSQVPRCWJZQK-UHFFFAOYSA-N 0.000 description 1
- YEHFKJFPRRUBNA-UHFFFAOYSA-N COC1=CC=CC=C1C.COC1=CC=CC=C1C Chemical compound COC1=CC=CC=C1C.COC1=CC=CC=C1C YEHFKJFPRRUBNA-UHFFFAOYSA-N 0.000 description 1
- NPBVQXIMTZKSBA-UHFFFAOYSA-N Chavibetol Natural products COC1=CC=C(CC=C)C=C1O NPBVQXIMTZKSBA-UHFFFAOYSA-N 0.000 description 1
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000005770 Eugenol Substances 0.000 description 1
- 238000005863 Friedel-Crafts acylation reaction Methods 0.000 description 1
- 239000005792 Geraniol Substances 0.000 description 1
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- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- UVMRYBDEERADNV-UHFFFAOYSA-N Pseudoeugenol Natural products COC1=CC(C(C)=C)=CC=C1O UVMRYBDEERADNV-UHFFFAOYSA-N 0.000 description 1
- 235000004789 Rosa xanthina Nutrition 0.000 description 1
- 241000109329 Rosa xanthina Species 0.000 description 1
- DOOTYTYQINUNNV-UHFFFAOYSA-N Triethyl citrate Chemical compound CCOC(=O)CC(O)(C(=O)OCC)CC(=O)OCC DOOTYTYQINUNNV-UHFFFAOYSA-N 0.000 description 1
- UAVFEMBKDRODDE-UHFFFAOYSA-N Vetiveryl acetate Chemical compound CC1CC(OC(C)=O)C=C(C)C2CC(=C(C)C)CC12 UAVFEMBKDRODDE-UHFFFAOYSA-N 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000002386 air freshener Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- GUUHFMWKWLOQMM-NTCAYCPXSA-N alpha-hexylcinnamaldehyde Chemical compound CCCCCC\C(C=O)=C/C1=CC=CC=C1 GUUHFMWKWLOQMM-NTCAYCPXSA-N 0.000 description 1
- GUUHFMWKWLOQMM-UHFFFAOYSA-N alpha-n-hexylcinnamic aldehyde Natural products CCCCCCC(C=O)=CC1=CC=CC=C1 GUUHFMWKWLOQMM-UHFFFAOYSA-N 0.000 description 1
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 1
- 229940062909 amyl salicylate Drugs 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 230000001166 anti-perspirative effect Effects 0.000 description 1
- 239000003213 antiperspirant Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229940007550 benzyl acetate Drugs 0.000 description 1
- 229960002903 benzyl benzoate Drugs 0.000 description 1
- JGQFVRIQXUFPAH-UHFFFAOYSA-N beta-citronellol Natural products OCCC(C)CCCC(C)=C JGQFVRIQXUFPAH-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- FZJUFJKVIYFBSY-UHFFFAOYSA-N bourgeonal Chemical compound CC(C)(C)C1=CC=C(CCC=O)C=C1 FZJUFJKVIYFBSY-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 235000000484 citronellol Nutrition 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- BLBJUGKATXCWET-UHFFFAOYSA-N cyclaprop Chemical compound C12CC=CC2C2CC(OC(=O)CC)C1C2 BLBJUGKATXCWET-UHFFFAOYSA-N 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- KSMVZQYAVGTKIV-UHFFFAOYSA-N decanal Chemical compound CCCCCCCCCC=O KSMVZQYAVGTKIV-UHFFFAOYSA-N 0.000 description 1
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
- XSNQECSCDATQEL-UHFFFAOYSA-N dihydromyrcenol Chemical compound C=CC(C)CCCC(C)(C)O XSNQECSCDATQEL-UHFFFAOYSA-N 0.000 description 1
- 229930008394 dihydromyrcenol Natural products 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- NYNCZOLNVTXTTP-UHFFFAOYSA-N ethyl 2-(1,3-dioxoisoindol-2-yl)acetate Chemical compound C1=CC=C2C(=O)N(CC(=O)OCC)C(=O)C2=C1 NYNCZOLNVTXTTP-UHFFFAOYSA-N 0.000 description 1
- 229960002217 eugenol Drugs 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- HIGQPQRQIQDZMP-UHFFFAOYSA-N geranil acetate Natural products CC(C)=CCCC(C)=CCOC(C)=O HIGQPQRQIQDZMP-UHFFFAOYSA-N 0.000 description 1
- 229940113087 geraniol Drugs 0.000 description 1
- HIGQPQRQIQDZMP-DHZHZOJOSA-N geranyl acetate Chemical compound CC(C)=CCC\C(C)=C\COC(C)=O HIGQPQRQIQDZMP-DHZHZOJOSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- WPFVBOQKRVRMJB-UHFFFAOYSA-N hydroxycitronellal Chemical compound O=CCC(C)CCCC(C)(C)O WPFVBOQKRVRMJB-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229930002839 ionone Natural products 0.000 description 1
- 150000002499 ionone derivatives Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- HEBMCVBCEDMUOF-UHFFFAOYSA-N isochromane Chemical compound C1=CC=C2COCCC2=C1 HEBMCVBCEDMUOF-UHFFFAOYSA-N 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 229930007744 linalool Natural products 0.000 description 1
- UWKAYLJWKGQEPM-UHFFFAOYSA-N linalool acetate Natural products CC(C)=CCCC(C)(C=C)OC(C)=O UWKAYLJWKGQEPM-UHFFFAOYSA-N 0.000 description 1
- 150000007931 macrolactones Chemical class 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- ZOCHHNOQQHDWHG-UHFFFAOYSA-N n-hexan-3-ol Natural products CCCC(O)CC ZOCHHNOQQHDWHG-UHFFFAOYSA-N 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000002674 ointment Substances 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- SATCULPHIDQDRE-UHFFFAOYSA-N piperonal Chemical compound O=CC1=CC=C2OCOC2=C1 SATCULPHIDQDRE-UHFFFAOYSA-N 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002453 shampoo Substances 0.000 description 1
- 238000001577 simple distillation Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- LMLRTJVTPAYATN-UHFFFAOYSA-N trichloromethyl acetate Chemical compound CC(=O)OC(Cl)(Cl)Cl LMLRTJVTPAYATN-UHFFFAOYSA-N 0.000 description 1
- 239000001069 triethyl citrate Substances 0.000 description 1
- VMYFZRTXGLUXMZ-UHFFFAOYSA-N triethyl citrate Natural products CCOC(=O)C(O)(C(=O)OCC)C(=O)OCC VMYFZRTXGLUXMZ-UHFFFAOYSA-N 0.000 description 1
- 235000013769 triethyl citrate Nutrition 0.000 description 1
- YOIAWAIKYVEKMF-UHFFFAOYSA-N trifluoromethanesulfonic acid Chemical compound OS(=O)(=O)C(F)(F)F.OS(=O)(=O)C(F)(F)F YOIAWAIKYVEKMF-UHFFFAOYSA-N 0.000 description 1
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 1
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 1
- 235000012141 vanillin Nutrition 0.000 description 1
- 229940117960 vanillin Drugs 0.000 description 1
- 239000000341 volatile oil Substances 0.000 description 1
- ZFNVDHOSLNRHNN-UHFFFAOYSA-N xi-3-(4-Isopropylphenyl)-2-methylpropanal Chemical compound O=CC(C)CC1=CC=C(C(C)C)C=C1 ZFNVDHOSLNRHNN-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
- C07C13/02—Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
- C07C13/16—Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with a six-membered ring
- C07C13/18—Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with a six-membered ring with a cyclohexane ring
- C07C13/19—Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with a six-membered ring with a cyclohexane ring substituted by unsaturated hydrocarbon groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
- C07C13/02—Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
- C07C13/16—Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with a six-membered ring
- C07C13/20—Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with a six-membered ring with a cyclohexene ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/03—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2
- C07C29/04—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2 by hydration of carbon-to-carbon double bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C35/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring
- C07C35/02—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring monocyclic
- C07C35/08—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring monocyclic containing a six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/07—Optical isomers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
Abstract
Description
【０００１】
技術分野
本発明は、新規な芳香化合物、それらの製造方法、及び、香料及び芳香性製品におけるそれらの使用、さらにその他の材料、特にその他の芳香化合物の製造における中間体としてのそれらの使用、に関する。
【０００２】
発明の開示
１つの観点において、本発明は、以下の構造を有するアルケンを提供するものである。
【０００３】
【化３】
簡便のため、本明細書において、このような物質を、“アルケン”、“新規なアルケン”、又は“本発明のアルケン”と記載する。
【０００５】
本発明のアルケンは、それぞれ、５−（２−メチルプロピル）−１−メチル−１−シクロヘキセン、１−メチリデン−３−（２−メチルプロピル）シクロヘキサン、３−（２−メチルプロピル）−１−メチル−１−シクロヘキセン、の３つの異性体を含み、本発明の範囲には、これらの個々の異性体、及び２或いは３の異性体の混合物も含まれる。
【０００６】
本発明のアルケンは、個別に及び集合的に興味深い芳香性又は香り特性（一般に花の、特に天然のバラ及び牡丹（ｐｅｏｎｉｌｅ）の）を示す。従って、当該アルケンは、幅広い種類の製品に香りを与え、強くし、又は改良すること等に用いることができ、そのような香料の全体の香りにその香り特性を付与する香料の成分（又は、芳香組成物）として用いることができる。本発明の目的では、香料は、芳香性物質の混合物を意味するものとして用い、所望ならば、適切な溶媒に混ぜられ又は溶解され、又は固体支持体に混ぜられ、当該香料は皮膚及び／又は、心地よい香りが必須であり望ましい全ての製品に所望の香りを付与するために用いられる。そのような製品の例は、布の洗濯用の粉洗剤、液体洗剤、錠剤洗剤、柔軟材、及びその他の布のケア製品；洗浄剤、及び家庭用の掃除、みがき洗い、殺菌のための製品；空気清浄剤、ルームスプレー、及びにおい玉（ｐｏｍａｎｄｅｒ）；せっけん、バス及びシャワージェル、シャンプー、ヘアコンディショナー、及びその他の個人用の洗浄製品；クリーム、軟こう、化粧水、髭剃り前又は後に用いるローション、スキンローション、及びその他のローション、化粧用パウダー、ボディデオドラント、及び防汗剤のような化粧品、等である。
【０００７】
香料において、本発明のアルケンと都合良く結合できるその他の芳香性物質は、例えば、エキス、エッセンシャルオイル、アブソリュート、レジノイド、樹脂、コンクリート等の天然物、さらに、飽和及び不飽和化合物、脂肪族、炭素環式、及びヘテロ環式化合物を含む、炭化水素、アルコール、アルデヒド、ケトン、エーテル、酸、エステル、アセタール、ケタール、ニトリル等の合成物である。
【０００８】
そのような芳香性物質は、例えば、Ｓ．Ａｒｃｔａｎｄｅｒ、Ｐｅｒｆｕｍｅ ａｎｄ Ｆｌａｖｏｒ Ｃｈｅｍｉｃａｌｓ（Ｍｏｎｔｃｌａｉｒ、Ｎ．Ｊ．、１９６９年）、Ｓ．Ａｒｃｔａｎｄｅｒ、Ｐｅｒｆｕｍｅ ａｎｄ Ｆｌａｖｏｒ Ｍａｔｅｒｉａｌｓ ｏｆ Ｎａｔｕｒａｌ Ｏｒｉｇｉｎ（Ｅｌｉｚａｂｅｔｈ、Ｎ．Ｊ．、１９６０年）、及び“Ｆｌａｖｏｒ ａｎｄ Ｆｒａｇｒｅｎｃｅ Ｍａｔｅｒｉａｌｓ−１９９１”、Ａｌｌｕｒｅｄ Ｐｕｂｌｉｓｈｉｎｇ Ｃｏ．Ｗｈｅａｔｏｎ、Ｉｌｌ．ＵＳＡ、に記載されている。
【０００９】
本発明のアルケンと組合せて用いることができる芳香性物質の例は、ゲラニオール、酢酸ゲラニル、リナロール、酢酸リナリル、テトラヒドロリナロール、シトロネロール、酢酸シトロネリル、ジヒドロミルセノール、酢酸ジヒドロミルセニル、テトラヒドロミルセノール、テルピネオール、酢酸テルピニル、ノポール、酢酸ノピル、２−フェニルエタノール、酢酸２−フェニルエチル、ベンジルアルコール、酢酸ベンジル、サリチル酸ベンジル、酢酸スリラリル、安息香酸ベンジル、サリチル酸アミル、ジメチルベンジルカルビノール、酢酸トリクロロメチルフェニルカルビニル、酢酸ｐ−ｔｅｒｔ−ブチル−シクロヘキシル、酢酸イソノニル、酢酸ベチベリル、ベチベロール、α−ヘキシル桂皮アルデヒド、２−メチル−３−（ｐ−ｔｅｒｔ−ブチルフェニル）プロパナール、２−メチル−３−（ｐ−イソプロピルフェニル）プロパナール、３−（ｐ−ｔｅｒｔ−ブチルフェニル）プロパナール、２，４−ジメチルシクロヘキシ−３−エニル−カルボキシアルデヒド、酢酸トリシクロデセニル、プロピオン酸トリシクロデセニル、４−（４−ヒドロキシ−４−メチルペンチル）−３−シクロヘキセンカルボキシアルデヒド、４−（４−メチル−３−ペンチル）−３−シクロヘキセンカルボキシアルデヒド、４−アセトキシ−３−ペンチル−テトラヒドロピラン、３−カルボキシメチル−２−ペンチルシクロペンタン、２−ｎ−ヘプチル−シクロペンタノン、３−メチル−２−ペンチル−２−シクロペンタノン、ｎ−デカナール、ｎ−ドデカナール、９−デセン−１−オール、イソ酪酸フェノキシエチル、フェニルアセトアルデヒドジメチルアセタール、フェニルアセトアルデヒドジエチルアセタール、ゲラニルニトリル、シトロネリルニトリル、酢酸セドリル、３−イソカンフィルシクロヘキサノール、セドリルメチルエーテル、イソロンギホラノン、オーベピンニトリル、オーベピン、ヘリオトロピン、クマリン、オイゲノール、バニリン、ジフェニルオキシド、ヒドロキシシトロネラール、イオノン、メチルイオノン、イソメチルイオノン、イロン、シス−３−ヘキサノール及びそのエステル、インダンムスク（ｍｕｓｋ）、テトラリンムスク、イソクロマンムスク、大環状ケトン、マクロラクトンムスク（ｍａｃｒｏｌａｃｔｏｎｅ ｍｕｓｋ）、ブラシジン酸エチレンである。
【００１０】
本発明のアルケンを含む香料について用いられ得る溶媒は、例えば、エタノール、イソプロパノール、ジエチレングリコールモノエチルエーテル、ジプロピレングリコール、フタル酸ジエチル、クエン酸トリエチル、ミリスチン酸イソプロピルである。
【００１１】
香料、又は香り付けされた製品に用いられ得る本発明のアルケンの量は、広い範囲内で変えることができ、それは、とりわけ、製品の性質、アルケンが用いられる香料におけるその他の成分の性質と量、及び、所望の嗅覚的効果に依存する。それゆえ、広い範囲を明確にすることができるのみであるが、しかし、当該技術分野における当業者が、特定の目的のために本発明のアルケンを用いることができるために十分な情報を提供する。香料において、本発明のアルケンが重量で０．０１％より多い量であれば、一般に、感知できる嗅覚的効果を有するであろう。典型的には、香料における本発明のアルケンの量は、重量で０．０１％乃至２５％であり、好ましくは重量で１％乃至５％である。製品に存在する本発明のアルケンの量は、香り付けされる製品に依存して、一般に、重量で１乃至１００００ｐｐｍであり、好ましくは重量で１０乃至１０００ｐｐｍである。
【００１２】
従って、さらなる観点では、本発明は嗅覚的に効果的な量の本発明のアルケンを含む香料を提供するものである。
【００１３】
本発明は、また、本発明のアルケンを含む芳香性製品を含む。
【００１４】
本発明のアルケンは、また、その他の化合物、特にその他の芳香化合物の製造における中間体として有用である。当該アルケンは、（非常に有用な芳香性物質である）３−（２−メチルプロピル）−１−メチルシクロヘキサノール（１−メチル−３−（２−メチルプロピル）シクロヘキサン−１−オールとも記載される）（ＷＯ９８／４７８４２参照）の製造において特に適用される（例えば、１以上のアルケンの水和によって）。
【００１５】
それゆえ、さらなる観点では、本発明の範囲には、本発明のアルケンを水和して１以上のシクロアルカノールを生成する工程を含むシクロアルカノールの製造方法であって、当該シクロアルカノールが、典型的には、以下の構造を有する当該方法が含まれる。
【００１６】
【化４】
ここで、Ｒ１はメチル又はエチル基、Ｒ２が水素原子、Ｒ３はエチル、プロピル、ブチル、イソブチル、又はイソアミル基、Ｒ４は水素原子、及びＲ５は水素原子又は、メチル、エチル、プロピル、ブチル、イソブチル、又はイソアミル基を表す。好ましくは、当該シクロアルカノールは３−（２−メチルプロピル）−１−メチルシクロヘキサノールである。
【００１８】
従って、本発明の範囲には、また、上述した方法により製造される、シクロアルカノール、好ましくは３−（２−メチルプロピル）−１−メチルシクロヘキサノールが含まれる。
【００１９】
本発明によるアルケンは、４−（２−メチルプロピル）−１−メトキシ−２−メチルシクロヘキサン、４−（２−メチルプロピル）−２−メチルシクロヘキサノール、又はそれらの混合物において行われる脱離によって、簡便に調製され得る。好ましくは、本発明のアルケンは、４−（２−メチルプロピル）−１−メトキシ−２−メチルシクロヘキサン（新規な飽和メチルエーテルである）、及び４−（２−メチルプロピル）−２−メチルシクロヘキサノール（４−イソブチル−２−メチルシクロヘキサノールとしても知られ、ＷＯ９９／５５８１１において開示されている公知のアルコールである）の混合物において行われる脱離によって調製される。これは、例えば、４−メチルベンゼンスルホン酸（ｐＴＳＡ）触媒及びシクロヘキサン溶媒を用いて行われる。この反応により、本発明における３つの異性体のアルケン混合物が生成する。反応のための適切なエーテルとアルコールの混合物は、４−（２−メチルプロピル）−１−メトキシ−２−メチルベンゼン及び当該エーテルとアルコールの混合物を与える１−（４−メトキシ−３−メチルフェニル）−２−メチル−１−プロパノンの触媒的水素化により、簡便に生成され得る。
【００２０】
結果として得られる異性体混合物は、芳香性物質としても、又はその他の化合物の調製における中間体としても用いることができる。さらに、異性体は、クロマトグラフィー又は蒸留のような公知の分離技術を用いること等により、分離され得る。例えば、１−メチリデン−３−（２−メチルプロピル）シクロヘキサンは、分留により、その他の２つの異性体である５−（２−メチルプロピル）−１−メチル−１−シクロヘキセン及び３−（２−メチルプロピル）−１−メチル−１−シクロヘキセンから分離することができる。
【００２１】
本発明は、さらに、説明のために以下の実施例において記載され、当該実施例には、本発明におけるアルケン混合物の製造のための３段階の工程、及びそれに続く第４の段階における、アルケン混合物からの３−（２−メチルプロピル）−１−メチルシクロヘキサノールの製造について記載する。
【００２２】
実施例１
以下の実施例における分析に利用したＧＣ／ＧＬＣの条件は、
ＧＣ： Ｈｅｗｌｅｔｔ Ｐａｃｋａｒｄ ＨＰ６８９０ ガスクロマトグラフ
カラム： ＨＰ−５（ＳＥ５４）３０ｍ ｘ ０．３２ｍｍ（内部直径）ｘ ０．２５μｍ ｄｆ （Ｈｅｗｌｅｔｔ Ｐａｃｋａｒｄより入手）
キャリヤーガス： 水素
溶媒／注入速度： アセトン、０．２μｌ
インジェクター： ２２０℃、スプリット６０：１
検出器： ＦＩＤ、２８０℃
温度プログラム： ７０℃（初期オーブン温度）、３分間保持、１００℃まで１０℃／分で上昇、その後２８０℃まで２５℃／分で上昇させ、４分間保持
段階１．フリーデル−クラフツアシル化
実験
１−メトキシ−２−メチルベンゼン（メチルアニソール）（２６１ｋｇ、純度９８．６％、２．１０９ｋｍｏｌ）及びトリフルオロメタンスルホン酸（ｔｒｉｆｌｉｃ ａｃｉｄ）（３２６ｇ、２．１７ｍｏｌ）（触媒）を１３６０リットルのガラス内張り汎用反応器に添加した。混合物を、窒素雰囲気下において１５０℃の温度まで攪拌しながら加熱した。一旦その温度で、１−メチルプロピオン酸無水物（３６５ｋｇ、２．３１ｋｍｏｌ）を、反応温度を１５０℃に保ちながら２時間の間、反応容器に徐々に添加した。混合物を、この温度でさらに１時間半攪拌した。４０℃まで冷却した後、触媒を固体炭酸ナトリウム（２３０ｇ、２．１６ｍｏｌ）で中和し、副生成物である２−メチルプロピオン酸を、減圧下（３０ｍＢａｒ）において１２０℃のポット温度に至るまで蒸留して除いた。得られた物質を５％ｗ／ｗ炭酸ナトリウム溶液（６０ｋｇ）で２回洗浄し、ＧＣｒｐａにより純度９３．９％の粗生成物、１−（４−メトキシ−３−メチルフェニル）−２−メチル−１−プロパノン（３８５ｋｇ、１．８８ｋｍｏｌ、１−メトキシ−２−メチルベンゼンに基づく分析により理論収率８９．２％）を得た。
【００２３】
蒸留
粗生成物（３８１．４ｋｇ、１．８６ｋｍｏｌ）を、５理論段数の充填カラムに通し、減圧蒸留により精製した。生成物である１−（４−メトキシ−３−メチルフェニル）−２−メチル−１−プロパノン（３４５．５ｋｇ、純度９７．７％ｒｐａ、１．７６ｋｍｏｌ）を８ｍＢａｒ、１３７−１４０℃において捕集し、融点２２℃において結晶化させた。その結果、蒸留された生成物の総収率は、１−メトキシ−２−メチルベンゼンに基づき８４．１％であった。
【００２４】
【化５】
段階２．水素化
実験
上記のようにして得た１−（４−メトキシ−３−メチルフェニル）−２−メチル−１−プロパノン（６０．０ｋｇ、ＧＣにより純度９７．３％、０．３０４ｋｍｏｌ）を、攪拌機及び水素供給を備えた１００リットルの高圧反応器に添加した。蒸留水（２５．０ｋｇ、１．３８９ｋｍｏｌ）、乳酸共触媒の８５％水溶液（２．０ｋｇ、１８．９ｍｏｌ）、及び水素化触媒（Ｔｙｐｅ８７Ｌ ｐａｓｔｅ ｅｘ Ｊｏｈｎｓｏｎ Ｍａｔｔｈｅｙの木炭上の５％パラジウム、１．２ｋｇ）を反応器に添加した。窒素と水素でパージした後、水素化の第１段階において、攪拌混合物を２０ｂａｒの水素雰囲気下に置き、水素ガスをさらに加えて２０ｂａｒゲージの圧力を保ちながら、１時間かけて１００℃の温度にした。この温度と圧力を、水素添加を効果的に終了させるまで、さらに１時間保持した。水素化の第２段階において、１４０℃−１５０℃まで加熱する前に、圧力を４８ｂａｒゲージまで上昇させた。この温度と圧力を、水素添加を効果的に終了させるまで、約６−１０時間保持した（反応時間は、触媒と供給原料の両方に依存する）。室温まで冷却した後、圧力を解放し、窒素パージの後、混合物を濾過し、水素化触媒を除去した。水層は、粗生成物（５５．４ｋｇ）から分離した。
【００２６】
粗生成物の詳細なＧＬＣ分析により、４−（２−メチルプロピル）−１−メトキシ−２−メチルシクロヘキサン及び４−（２−メチルプロピル）−２−メチルシクロヘキサノールの異性体混合物が生成物の９３．３％であることがわかった。この分析によって、これらの所望の生成物の総量は０．２９ｋｍｏｌであり、それは１−（４−メトキシ−３−メチルフェニル）−２−メチル−１−プロパノンに基づく９２．８％の理論収率と一致した。
【００２７】
蒸留
蒸留は、必須ではないが、約５理論段数の短い充填カラム上の単純な蒸留によって、生成物であるエーテル及びアルコールは共に、水、ライトヘッド（ｌｉｇｈｔ ｈｅａｄｓ）、及び残留物から有効に分離される。典型的には、粗４−（２−メチルプロピル）−１−メトキシ−２−メチルシクロヘキサン／４−（２−メチルプロピル）−２−メチルシクロヘキサノール（５５．４ｋｇ、ＧＣにより純度９３．３％ｒｐａ、０．２９ｋｍｏｌ）から、９８−１１６℃／３０ｍＢａｒの範囲の沸点を有する４−（２−メチルプロピル）−１−メトキシ−２−メチルシクロヘキサン及び４−（２−メチルプロピル）−２−メチルシクロヘキサノールの異性体混合物（５２．４ｋｇ、ＧＣにより純度９６．０％、０．２８ｋｍｏｌ）が得られた。
【００２８】
【化６】
以下に示す多数の異なるエーテル異性体が存在する。
【００３０】
【化７】
以下に示す多数の類似するアルコール異性体が存在する。
【００３２】
【化８】
段階３．脱離
実験
上記のようにして得た４−（２−メチルプロピル）−１−メトキシ−２−メチルシクロヘキサン及び４−（２−メチルプロピル）−２−メチルシクロヘキサノール（４６．３ｋｇ、ＧＣにより純度９２．６％ｒｐａ、〜０．２４ｋｍｏｌ）、４−メチルベンゼンスルホン酸一水和物（ｐＴＳＡ触媒）（１．４ｋｇ、７．４ｍｏｌ）、及びシクロヘキサン（１０．０ｋｇ）を、１００リットルのガラス内張り汎用反応器に添加した。攪拌される混合物は、窒素雰囲気下で１５０℃の温度まで加熱した。上部のシクロヘキサン層をフラスコに戻し、シクロヘキサン／水／メタノール共沸混合物をＤｅａｎ＆Ｓｔａｒｋにおいて除去し、上部のシクロヘキサン層をフラスコに戻した。シクロヘキサンの量は、フラスコの温度を１５０℃−１５５℃に保つため調節した。これらの条件を８時間保持した。４０℃まで冷却した後、５％ｗ／ｗ炭酸ナトリウム溶液（９．０ｋｇ）で２回洗浄し、脱水した。得られた粗生成物は、微量の１−メチリデン−３−（２−メチルプロピル）シクロヘキサンを含む３−（２−メチルプロピル）−１−メチル−１−シクロヘキセン／５−（２−メチルプロピル）−１−メチル−１−シクロヘキセン（典型的に、１：２の比率）が４０．４ｋｇ、ＧＣにより純度６６．９％ｒｐａ（２７．０ｋｇ、０．１８ｋｍｏｌ）、及び、未反応の出発物質がＧＣにより９．６％ｒｐａ（３．９ｋｇ、０．０２ｍｏｌ）であった。その結果、この反応の化学的収率は７５％であり、選択性は８２％であった。
【００３４】
蒸留
ＧＣにより純度６４．５％ｒｐａの所望のアルケンを含む、このような２つの反応からの粗生成物（８０．４ｋｇ）を、２０：１の還流比で３０理論段数の充填カラムを経た、減圧下における注意深い分留により精製した。３−（２−メチルプロピル）−１−メチル−１−シクロヘキセンと５−（２−メチルプロピル）−１−メチル−１−シクロヘキセンの混合物は、８８−９３℃／３２−４０ｍＢａｒの範囲で捕集した。精製した生成物（６１ｋｇ）は、８１．５％ｒｐａの所望のアルケンを含み、これは９６％の蒸留収率と対応する。生成物は、常温で液体であった。
【００３５】
未反応の出発物質は蒸留残留物中に残っていた。
【００３６】
【化９】
段階４．水和
実験
上記のようにして得た、少量の１−メチリデン−３−（２−メチルプロピル）シクロヘキサンを含む３−（２−メチルプロピル）−１−メチル−１−シクロヘキセンと５−（２−メチルプロピル）−１−メチル−１−シクロヘキセンの混合物（３０．１ｋｇ、“純度”８２．１％ｒｐａ、０．１６ｋｍｏｌ）を、１００リットルのガラス内張り汎用反応器に添加した。３−（２−メチルプロピル）−１−メチルシクロヘキサノール（０．３ｋｇ、１．７６ｍｏｌ）を添加した（この少量の所望の最終生成物は、相転移剤として働き、及び反応の開始を促す）。攪拌された混合物を−５℃まで冷却し、温度を−６から−３℃の範囲に保ちながら、７６％ｗ／ｗの硫酸（２０．４ｋｇ、０．１５８ｋｍｏｌ）を５時間かけてゆっくり添加した。酸添加後さらに１時間の間、攪拌された混合物をこの温度範囲に保った。温度を２５℃以下に保ちながら、混合物をよく攪拌された冷却容器中の水（８０．０ｋｇ、４．４ｋｍｏｌ）にゆっくり添加し、その後、下方の水層を分離した。温度を２５℃以下に保ちながら、有機層を水（１１．０ｋｇ）で洗浄した。残存する酸触媒は、温度を３０℃以下に保ちながら、反応混合物を５％水酸化ナトリウム溶液で洗浄することにより中和した。得られた生成物を、５０℃−５５℃において水（１０ｋｇ）で２回洗浄し、粗生成物（３−（２−メチルプロピル）−１−メチルシクロヘキサノール）（３０．８ｋｇ）を得た。ＧＬＣ分析により、粗生成物は、トランス及びシス異性体の混合物である純粋な、５２．５５％ｒｐａ（０．０９５ｋｍｏｌ）の３−（２−メチルプロピル）−１−メチルシクロヘキサノールを含むことがわかった。これは、３−（２−メチルプロピル）−１−メチル−１−シクロヘキセン／５−（２−メチルプロピル）−１−メチル−１−シクロヘキセンに基づく５９．１％の化学収率に対応する。
【００３８】
蒸留
粗生成物（３０．８ｋｇ、０．０９５ｋｍｏｌ）を、約１５理論段数の充填カラムを経た減圧下における分留により精製した。生成物３−（２−メチルプロピル）−１−メチルシクロヘキサノール（１５．２８ｋｇ、ＧＣｒｐａにより純度９８．７％、０．０８９ｋｍｏｌ）は、９８−１００℃、１５ｍＢａｒにおいて捕集した。芳香性物質（Ｐｅｒｆｕｍｅｒｙ Ｑｕａｌｉｔｙ ｍａｔｅｒｉａｌ）の総収率は、３−（２−メチルプロピル）−１−メチル−１−シクロヘキセン／５−（２−メチルプロピル）−１−メチル−１−シクロヘキセンに基づいて、５５．１％ｗ／ｗであった。生成物３−（２−メチルプロピル）−１−メチルシクロヘキサノールは、約３５−４５％のシス異性体と約５５−６５％のトランス異性体の混合物であった。当該生成物は、２０−２５℃の融点において凝固し得る。
【００３９】
【化１０】
TECHNICAL FIELD The present invention relates to novel fragrance compounds, processes for their preparation and their use in perfumery and fragrance products, as well as other materials, especially as intermediates in the preparation of other fragrance compounds Use of.
[0002]
DISCLOSURE OF THE INVENTION In one aspect, the present invention provides an alkene having the following structure.
[0003]
Embedded image
For convenience, such materials are referred to herein as "alkenes,""newalkenes," or "alkenes of the present invention."
[0005]
The alkene of the present invention is 5- (2-methylpropyl) -1-methyl-1-cyclohexene, 1-methylidene-3- (2-methylpropyl) cyclohexane, 3- (2-methylpropyl) -1-, respectively. Methyl-1-cyclohexene, and the scope of the present invention also includes these individual isomers and mixtures of the two or three isomers.
[0006]
The alkenes of the present invention individually and collectively exhibit interesting aromatic or scent characteristics (generally of flowers, especially of natural roses and peonyles). Thus, the alkene can be used to impart, enhance, or improve a wide variety of products, including perfume ingredients (or, (Fragrance composition). For the purposes of the present invention, fragrance is used to mean a mixture of fragrances, if desired mixed or dissolved in a suitable solvent or mixed with a solid support, wherein the fragrance is applied to the skin and / or It is used to impart a desired scent to all products where a pleasant scent is essential and desired. Examples of such products are laundry detergents, liquid detergents, tablet detergents, softeners and other fabric care products for washing laundry; cleaning agents and products for household cleaning, polishing and disinfection. Air fresheners, room sprays, and pomanders; soaps, bath and shower gels, shampoos, hair conditioners, and other personal cleaning products; creams, ointments, lotions, lotions to use before or after shaving. , Skin lotions and other lotions, cosmetic powders, body deodorants, and cosmetics such as antiperspirants.
[0007]
In fragrances, other aromatic substances that can be conveniently combined with the alkene of the present invention include, for example, extracts, essential oils, absolutes, resinoids, resins, natural products such as concrete, and also saturated and unsaturated compounds, aliphatics, carbocycles. Compounds of the formula and heterocyclic compounds, such as hydrocarbons, alcohols, aldehydes, ketones, ethers, acids, esters, acetals, ketals, nitriles and the like.
[0008]
Such aromatic substances are described, for example, in S.A. Arctander, Perfume and Flavor Chemicals (Montclair, NJ, 1969); Arctander, Perfume and Flavor Materials of Natural Origin (Elizabeth, NJ, 1960), and "Flavor and Fragrance Materials-1991", Allured Publishing. Wheaton, Ill. USA.
[0009]
Examples of aromatic substances that can be used in combination with the alkene of the present invention include geraniol, geranyl acetate, linalool, linalyl acetate, tetrahydrolinalool, citronellol, citronellyl acetate, dihydromyrcenol, dihydromyrcenyl acetate, tetrahydromyrcene. Nol, terpineol, terpinyl acetate, nopol, nopyr acetate, 2-phenylethanol, 2-phenylethyl acetate, benzyl alcohol, benzyl acetate, benzyl salicylate, thrillylyl acetate, benzyl benzoate, amyl salicylate, dimethylbenzylcarbinol, trichloromethyl acetate Phenylcarbinyl, p-tert-butyl-cyclohexyl acetate, isononyl acetate, vetiveryl acetate, vetiverol, α-hexylcinnamic aldehyde, 2-methyl-3- (p-te t-butylphenyl) propanal, 2-methyl-3- (p-isopropylphenyl) propanal, 3- (p-tert-butylphenyl) propanal, 2,4-dimethylcyclohex-3-enyl-carboxaldehyde , Tricyclodecenyl acetate, tricyclodecenyl propionate, 4- (4-hydroxy-4-methylpentyl) -3-cyclohexenecarboxaldehyde, 4- (4-methyl-3-pentyl) -3-cyclohexene Carboxaldehyde, 4-acetoxy-3-pentyl-tetrahydropyran, 3-carboxymethyl-2-pentylcyclopentane, 2-n-heptyl-cyclopentanone, 3-methyl-2-pentyl-2-cyclopentanone, n -Decanal, n-dodecanal, 9-decene-1-ol, iso- Phenoxyethyl butyrate, phenylacetaldehyde dimethyl acetal, phenylacetaldehyde diethyl acetal, geranyl nitrile, citronellyl nitrile, sedolyl acetate, 3-isocamphylcyclohexanol, sedolyl methyl ether, isolongifolanone, ovepinnitrile, ovepin, heliotropin Coumarin, eugenol, vanillin, diphenyl oxide, hydroxycitronellal, ionone, methylionone, isomethylionone, iron, cis-3-hexanol and its esters, indan musk (musk), tetralin musk, isochroman musk, macrocyclic Ketones, macrolactone musks, and ethylene brassic acid.
[0010]
Solvents that can be used for the alkene-containing flavors of the present invention are, for example, ethanol, isopropanol, diethylene glycol monoethyl ether, dipropylene glycol, diethyl phthalate, triethyl citrate, isopropyl myristate.
[0011]
The amount of the alkene of the present invention that can be used in a fragrance or scented product can vary within wide limits, including, among other things, the nature of the product, the nature and amount of other ingredients in the fragrance in which the alkene is used. And the desired olfactory effect. Therefore, it is only possible to clarify the broad scope, but provides sufficient information for those skilled in the art to be able to use the alkenes of the invention for specific purposes. . In perfumery, an alkene of the present invention in an amount greater than 0.01% by weight will generally have a noticeable olfactory effect. Typically, the amount of the alkene of the present invention in the perfume is from 0.01% to 25% by weight, preferably from 1% to 5% by weight. The amount of the inventive alkene present in the product is generally between 1 and 10000 ppm by weight, preferably between 10 and 1000 ppm by weight, depending on the product to be perfumed.
[0012]
Thus, in a further aspect, the present invention provides a fragrance comprising an olfactory effective amount of an alkene of the present invention.
[0013]
The present invention also includes fragrance products comprising the alkene of the present invention.
[0014]
The alkenes of the present invention are also useful as intermediates in the preparation of other compounds, especially other aromatic compounds. The alkene is also described as 3- (2-methylpropyl) -1-methylcyclohexanol (1-methyl-3- (2-methylpropyl) cyclohexane-1-ol, which is a very useful aromatic substance). (See, for example, WO 98/47842) (eg, by hydration of one or more alkenes).
[0015]
Therefore, in a further aspect, within the scope of the present invention is a process for producing a cycloalkanol comprising the step of hydrating an alkene of the present invention to produce one or more cycloalkanols, wherein the cycloalkanol is typically Includes the method having the following structure.
[0016]
Embedded image
Here, R 1 is a methyl or ethyl group, R 2 is a hydrogen atom, R 3 is an ethyl, propyl, butyl, isobutyl, or isoamyl group, R 4 is a hydrogen atom, and R 5 is a hydrogen atom or methyl, ethyl, Represents a propyl, butyl, isobutyl, or isoamyl group. Preferably, the cycloalkanol is 3- (2-methylpropyl) -1-methylcyclohexanol.
[0018]
Accordingly, the scope of the present invention also includes cycloalkanols, preferably 3- (2-methylpropyl) -1-methylcyclohexanol, prepared by the method described above.
[0019]
The alkene according to the invention can be obtained by elimination carried out in 4- (2-methylpropyl) -1-methoxy-2-methylcyclohexane, 4- (2-methylpropyl) -2-methylcyclohexanol or mixtures thereof, It can be conveniently prepared. Preferably, the alkene of the present invention comprises 4- (2-methylpropyl) -1-methoxy-2-methylcyclohexane (which is a novel saturated methyl ether) and 4- (2-methylpropyl) -2-methylcyclohexane. It is prepared by elimination performed on a mixture of hexanol (also known as 4-isobutyl-2-methylcyclohexanol, which is a known alcohol disclosed in WO 99/55811). This is done, for example, using a 4-methylbenzenesulfonic acid (pTSA) catalyst and a cyclohexane solvent. This reaction produces an alkene mixture of the three isomers of the present invention. A suitable mixture of ether and alcohol for the reaction is 4- (2-methylpropyl) -1-methoxy-2-methylbenzene and 1- (4-methoxy-3-methylphenyl) to give a mixture of the ether and alcohol. ) Can be conveniently produced by catalytic hydrogenation of 2-methyl-1-propanone.
[0020]
The resulting mixture of isomers can be used as an aromatic or as an intermediate in the preparation of other compounds. Further, isomers can be separated, such as by using known separation techniques such as chromatography or distillation. For example, 1-methylidene-3- (2-methylpropyl) cyclohexane can be separated by fractional distillation into two other isomers, 5- (2-methylpropyl) -1-methyl-1-cyclohexene and 3- (2 -Methylpropyl) -1-methyl-1-cyclohexene.
[0021]
The present invention is further described in the following examples for illustration, in which a three-step process for the preparation of an alkene mixture according to the invention, followed by a fourth step, is carried out in an alkene mixture. The production of 3- (2-methylpropyl) -1-methylcyclohexanol from is described.
[0022]
Example 1
The conditions of GC / GLC used for the analysis in the following examples are as follows:
GC: Hewlett Packard HP6890 gas chromatograph column (available from Hewlett Packard) HP-5 (SE54 ) 30m x 0.32mm ( internal diameter) x 0.25 [mu] m d f
Carrier gas: hydrogen solvent / injection rate: acetone, 0.2 μl
Injector: 220 ° C, split 60: 1
Detector: FID, 280 ° C
Temperature program: 70 ° C (initial oven temperature), hold for 3 minutes, increase to 100 ° C at 10 ° C / minute, then increase to 280 ° C at 25 ° C / minute, hold for 4 minutes
Step 1. Friedel-Crafts acylation
Experiment 1-Methoxy-2-methylbenzene (methylanisole) (261 kg, purity 98.6%, 2.109 kmol) and trifluoromethanesulfonic acid (triflic acid) (326 g, 2.17 mol) (catalyst) in 1360 liter glass The lining was added to a general-purpose reactor. The mixture was heated with stirring to a temperature of 150 ° C. under a nitrogen atmosphere. Once at that temperature, 1-methylpropionic anhydride (365 kg, 2.31 kmol) was slowly added to the reaction vessel over 2 hours while maintaining the reaction temperature at 150 ° C. The mixture was stirred at this temperature for a further 1.5 hours. After cooling to 40 ° C., the catalyst was neutralized with solid sodium carbonate (230 g, 2.16 mol) and the by-product 2-methylpropionic acid was reduced under reduced pressure (30 mBar) to a pot temperature of 120 ° C. Distilled off. The resulting material was washed twice with 5% w / w sodium carbonate solution (60 kg) and the crude product, 1- (4-methoxy-3-methylphenyl) -2-methyl, 93.9% pure by GCrpa. -1-propanone (385 kg, 1.88 kmol, theoretical yield 89.2% by analysis based on 1-methoxy-2-methylbenzene) was obtained.
[0023]
Distillation The crude product (381.4 kg, 1.86 kmol) was passed through a packed column of 5 theoretical plates and purified by distillation under reduced pressure. The product 1- (4-methoxy-3-methylphenyl) -2-methyl-1-propanone (345.5 kg, purity 97.7% rpa, 1.76 kmol) was collected at 8 mBar and 137-140 ° C. Then, it was crystallized at a melting point of 22 ° C. As a result, the total yield of the distilled product was 84.1% based on 1-methoxy-2-methylbenzene.
[0024]
Embedded image
Step 2. Hydrogenation
Experiment 1- (4-methoxy-3-methylphenyl) -2-methyl-1-propanone (60.0 kg, purity 97.3% by GC, 0.304 kmol) obtained as described above was used. , A stirrer and a hydrogen supply to a 100 liter high pressure reactor. Distilled water (25.0 kg, 1.389 kmol), 85% aqueous solution of lactic acid cocatalyst (2.0 kg, 18.9 mol), and hydrogenation catalyst (Type 87L paste ex Johnson Matthey 5% palladium on charcoal, 1.2 kg ) Was added to the reactor. After purging with nitrogen and hydrogen, in the first stage of the hydrogenation, the stirred mixture is placed under a 20 bar hydrogen atmosphere, the hydrogen gas is further added and the temperature is raised to 100 ° C. over 1 hour while maintaining the pressure at 20 bar gauge. did. This temperature and pressure were maintained for an additional hour until the hydrogenation was effectively terminated. In the second stage of the hydrogenation, the pressure was increased to 48 bar gauge before heating to 140-150 ° C. The temperature and pressure were held for about 6-10 hours until the hydrogenation was effectively terminated (reaction time depends on both catalyst and feed). After cooling to room temperature, the pressure was released and after a nitrogen purge, the mixture was filtered to remove the hydrogenation catalyst. The aqueous layer was separated from the crude product (55.4kg).
[0026]
Detailed GLC analysis of the crude product indicated that an isomer mixture of 4- (2-methylpropyl) -1-methoxy-2-methylcyclohexane and 4- (2-methylpropyl) -2-methylcyclohexanol was obtained. It turned out to be 93.3%. By this analysis, the total amount of these desired products is 0.29 kmol, which is a 92.8% theoretical yield based on 1- (4-methoxy-3-methylphenyl) -2-methyl-1-propanone And matched.
[0027]
Distillation Distillation is not essential, but by simple distillation on a short packed column of about 5 theoretical plates, the product ether and alcohol both contain water, light heads, and residue. Effectively separated from Typically, crude 4- (2-methylpropyl) -1-methoxy-2-methylcyclohexane / 4- (2-methylpropyl) -2-methylcyclohexanol (55.4 kg, 93.3% pure by GC) rpa, 0.29 kmol) and 4- (2-methylpropyl) -1-methoxy-2-methylcyclohexane and 4- (2-methylpropyl) -2-methyl with boiling points in the range 98-116 ° C./30 mBar. An isomer mixture of cyclohexanol (52.4 kg, purity 96.0% by GC, 0.28 kmol) was obtained.
[0028]
Embedded image
There are a number of different ether isomers shown below.
[0030]
Embedded image
There are a number of similar alcohol isomers shown below.
[0032]
Embedded image
Step 3. Detachment
Experiment 4- (2-methylpropyl) -1-methoxy-2-methylcyclohexane and 4- (2-methylpropyl) -2-methylcyclohexanol obtained as described above (46.3 kg, GC 92.6% rpa, ~ 0.24 kmol), 4-methylbenzenesulfonic acid monohydrate (pTSA catalyst) (1.4 kg, 7.4 mol), and cyclohexane (10.0 kg) in 100 liters. Added to glass lined general purpose reactor. The stirred mixture was heated to a temperature of 150 ° C. under a nitrogen atmosphere. The upper cyclohexane layer was returned to the flask, the cyclohexane / water / methanol azeotrope was removed at Dean & Stark, and the upper cyclohexane layer was returned to the flask. The amount of cyclohexane was adjusted to keep the temperature of the flask between 150C and 155C. These conditions were maintained for 8 hours. After cooling to 40 ° C., it was washed twice with 5% w / w sodium carbonate solution (9.0 kg) and dehydrated. The obtained crude product is 3- (2-methylpropyl) -1-methyl-1-cyclohexene / 5- (2-methylpropyl) containing a trace amount of 1-methylidene-3- (2-methylpropyl) cyclohexane. 40.4 kg of -1-methyl-1-cyclohexene (typically 1: 2 ratio), 66.9% rpa by GC (27.0 kg, 0.18 kmol), and unreacted starting material It was 9.6% rpa (3.9 kg, 0.02 mol) by GC. As a result, the chemical yield of this reaction was 75%, and the selectivity was 82%.
[0034]
The crude product from such two reactions (80.4 kg) containing the desired alkene with a purity of 64.5% rpa by distillation GC was passed through a packed column of 30 theoretical plates at a reflux ratio of 20: 1, Purified by careful fractional distillation under reduced pressure. A mixture of 3- (2-methylpropyl) -1-methyl-1-cyclohexene and 5- (2-methylpropyl) -1-methyl-1-cyclohexene is collected in the range of 88-93 ° C./32-40 mBar. did. The purified product (61 kg) contains 81.5% rpa of the desired alkene, which corresponds to a distillation yield of 96%. The product was liquid at room temperature.
[0035]
Unreacted starting material remained in the distillation residue.
[0036]
Embedded image
Step 4. hydration
Experiment 3- (2-methylpropyl) -1-methyl-1-cyclohexene containing a small amount of 1-methylidene-3- (2-methylpropyl) cyclohexane, obtained as described above, and 5- ( A mixture of 2-methylpropyl) -1-methyl-1-cyclohexene (30.1 kg, "purity" 82.1% rpa, 0.16 kmol) was added to a 100 liter glass lined general purpose reactor. 3- (2-Methylpropyl) -1-methylcyclohexanol (0.3 kg, 1.76 mol) was added (this small amount of the desired end product acts as a phase transfer agent and facilitates the start of the reaction). . The stirred mixture was cooled to −5 ° C. and 76% w / w sulfuric acid (20.4 kg, 0.158 kmol) was added slowly over 5 hours, keeping the temperature in the range of −6 to −3 ° C. . The stirred mixture was kept in this temperature range for an additional hour after the acid addition. While keeping the temperature below 25 ° C., the mixture was slowly added to water (80.0 kg, 4.4 kmol) in a well-stirred cooling vessel, and then the lower aqueous layer was separated. The organic layer was washed with water (11.0 kg) while maintaining the temperature at 25 ° C. or lower. The remaining acid catalyst was neutralized by washing the reaction mixture with a 5% sodium hydroxide solution while maintaining the temperature at 30 ° C. or lower. The obtained product was washed twice with water (10 kg) at 50 ° C. to 55 ° C. to obtain a crude product (3- (2-methylpropyl) -1-methylcyclohexanol) (30.8 kg). . By GLC analysis, the crude product may contain pure 52.55% rpa (0.095 kmol) of 3- (2-methylpropyl) -1-methylcyclohexanol, which is a mixture of trans and cis isomers. all right. This corresponds to a chemical yield of 59.1% based on 3- (2-methylpropyl) -1-methyl-1-cyclohexene / 5- (2-methylpropyl) -1-methyl-1-cyclohexene.
[0038]
Distillation The crude product (30.8 kg, 0.095 kmol) was purified by fractional distillation under reduced pressure through a packed column of about 15 theoretical plates. The product, 3- (2-methylpropyl) -1-methylcyclohexanol (15.28 kg, 98.7% pure by GCrpa, 0.089 kmol) was collected at 98-100 ° C. and 15 mBar. The total yield of perfumery quality material is based on 3- (2-methylpropyl) -1-methyl-1-cyclohexene / 5- (2-methylpropyl) -1-methyl-1-cyclohexene. , 55.1% w / w. The product, 3- (2-methylpropyl) -1-methylcyclohexanol, was a mixture of about 35-45% cis isomer and about 55-65% trans isomer. The product may solidify at a melting point of 20-25 ° C.
[0039]
Embedded image
Claims (11)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP00306941 | 2000-08-14 | ||
| EP00306941.6 | 2000-08-14 | ||
| PCT/GB2001/003614 WO2002014243A1 (en) | 2000-08-14 | 2001-08-10 | Novel fragrance compounds |
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| Publication Number | Publication Date |
|---|---|
| JP2004506030A true JP2004506030A (en) | 2004-02-26 |
| JP5238116B2 JP5238116B2 (en) | 2013-07-17 |
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| JP2002519343A Expired - Lifetime JP5238116B2 (en) | 2000-08-14 | 2001-08-10 | New aromatic compounds |
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| US (1) | US20030176313A1 (en) |
| EP (1) | EP1309529B1 (en) |
| JP (1) | JP5238116B2 (en) |
| AT (1) | ATE283831T1 (en) |
| DE (1) | DE60107580T2 (en) |
| ES (1) | ES2231531T3 (en) |
| MX (1) | MXPA03001378A (en) |
| WO (1) | WO2002014243A1 (en) |
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|---|---|---|---|---|
| JP2004506034A (en) * | 2000-08-14 | 2004-02-26 | クエスト・インターナショナル・ビー・ブイ | Production of 3-alkylcycloalkanol |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE10058459A1 (en) | 2000-11-24 | 2002-06-06 | Haarmann & Reimer Gmbh | rhinologically |
| DE102004054620A1 (en) * | 2004-11-11 | 2006-06-08 | Henkel Kgaa | Geranonitrile substitute |
| ES2273592B1 (en) * | 2005-08-29 | 2008-04-01 | Sensient Fragrances, S.A. | ELIMINATING COMPOSITION OF THE BAD ODORS. |
| GB0710703D0 (en) | 2007-06-05 | 2007-07-18 | Givaudan Sa | Organic compounds |
| BR112014000685A2 (en) * | 2011-07-15 | 2017-11-21 | Momentive Performance Mat Inc | trivinyl cyclohexane stereoisomeric compositions and processes for preparing same |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998047842A1 (en) * | 1997-04-23 | 1998-10-29 | Quest International B.V. | Perfumes comprising 3-alkylcycloalkanols |
| JP2004506034A (en) * | 2000-08-14 | 2004-02-26 | クエスト・インターナショナル・ビー・ブイ | Production of 3-alkylcycloalkanol |
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| US5089469A (en) * | 1991-04-25 | 1992-02-18 | International Flavors & Fragrances Inc. | Bisabolene-containing composition, process for preparing same, organoleptic uses thereof and uses thereof as insect repellent |
-
2001
- 2001-08-10 MX MXPA03001378A patent/MXPA03001378A/en active IP Right Grant
- 2001-08-10 DE DE60107580T patent/DE60107580T2/en not_active Expired - Lifetime
- 2001-08-10 JP JP2002519343A patent/JP5238116B2/en not_active Expired - Lifetime
- 2001-08-10 ES ES01956673T patent/ES2231531T3/en not_active Expired - Lifetime
- 2001-08-10 WO PCT/GB2001/003614 patent/WO2002014243A1/en active IP Right Grant
- 2001-08-10 EP EP01956673A patent/EP1309529B1/en not_active Expired - Lifetime
- 2001-08-10 AT AT01956673T patent/ATE283831T1/en not_active IP Right Cessation
- 2001-08-10 US US10/344,370 patent/US20030176313A1/en not_active Abandoned
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998047842A1 (en) * | 1997-04-23 | 1998-10-29 | Quest International B.V. | Perfumes comprising 3-alkylcycloalkanols |
| JP2004506034A (en) * | 2000-08-14 | 2004-02-26 | クエスト・インターナショナル・ビー・ブイ | Production of 3-alkylcycloalkanol |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004506034A (en) * | 2000-08-14 | 2004-02-26 | クエスト・インターナショナル・ビー・ブイ | Production of 3-alkylcycloalkanol |
Also Published As
| Publication number | Publication date |
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| WO2002014243A1 (en) | 2002-02-21 |
| EP1309529A1 (en) | 2003-05-14 |
| DE60107580T2 (en) | 2005-05-25 |
| ES2231531T3 (en) | 2005-05-16 |
| US20030176313A1 (en) | 2003-09-18 |
| JP5238116B2 (en) | 2013-07-17 |
| DE60107580D1 (en) | 2005-01-05 |
| EP1309529B1 (en) | 2004-12-01 |
| MXPA03001378A (en) | 2003-06-06 |
| ATE283831T1 (en) | 2004-12-15 |
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